Polymerization processes for olefins

ABSTRACT

Certain olefins such as ethylene, α-olefins and cyclopentene can be polymerized by using catalyst system containing a nickel or palladium α-diimine complex, a metal containing hydrocarbylation compound, and a selected Lewis acid, or a catalyst system containing certain nickel  II! or palladium  II! compounds, an α-diimine, a metal containing hydrocarbylation compound, and optionally a selected Lewis acid. The process advantageously produces polyolefins useful for molding resins, films, elastomers and other uses.

This application claims the benefit of U.S. Provisional Application No.60/022,295 filed Jul. 23, 1996, and U.S. Provisional Application No.60/022,796, filed Jul. 30, 1996.

This application claims the benefit of U.S. Provisional Application No.60/022,295 filed Jul. 23, 1996, and U.S. Provisional Application No.60/022,796, filed Jul. 30, 1996.

FIELD OF THE INVENTION

Disclosed herein are processes for polymerizing selected olefins, bycontacting them with certain nickel or palladium compounds, otherselected compounds, and if the nickel or palladium compound is notalready an α-diimine complex, a free α-diimine.

TECHNICAL BACKGROUND

Polyolefins are important items of commerce, many thousands of tonsbeing produced annually. They are useful in many applications dependingupon their particular properties, for instance as molding resins,fibers, films useful in packaging and/or electronics, elastomers, andmany others. There are many known polymerization processes for producingpolyolefins, but given the importance of these polymers, improvedprocesses are constantly being sought.

L. K. Johnson, et. al., J. Am. Chem. Soc., vol. 117, p. 6414-6415(1995), and L. K. Johnson, et al., J. Am. Chem. Soc., vol. 118, p.267-268 (1996) describe the polymerization of olefins using certainα-diimine complexes. Neither of these references describes apolymerization process using the starting materials described herein.

SUMMARY OF THE INVENTION

Described herein is a first process for the polymerization of olefins,comprising, contacting, at a temperature of about -100° C. to about+200° C., a Ni (II) or Pd (II) complex of (I), ##STR1## a metalcontaining hydrocarbylation compound, and a compound (II) selected fromthe group consisting of B(C₆ F₅)₃, AlCl₃, AlBr₃, Al(OTf)₃, and (R¹³ R¹⁴R¹⁵ C)Y, with an olefin, wherein:

said olefin is selected from the group consisting of ethylene, an olefinof the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclobutene, cyclopentene,and a norbornene;

R² and R⁵ are each independently aryl or substituted aryl, provided inboth R² and R⁵ at least one of the carbon atoms bound to a carbon atombound directly to an imino nitrogen atom does not have any hydrogenatoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a carbocyclic ring;

R¹³, R¹⁴ and R¹⁵ are each independently aryl or substituted aryl;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms; and

Y is a relatively noncoordinating anion.

This invention also concerns a second process for the polymerization ofolefins, comprising, contacting a Ni (II) or Pd (II) salt with (I),##STR2## a metal containing hydrocarbylation compound, and optionally acompound (II) selected from the group consisting of B(C₆ F₅)₃, AlCl₃,AlBr₃, Al(OTf)₃, and (R¹³ R¹⁴ R¹⁵ C)Y, with an olefin, wherein:

said Ni (II) or Pd (II) salt is selected from the group consisting ofNi(O₂ CR⁷)₂, Ni R⁸ COCH═C(O)R⁸ !₂, NiX₂, L¹ L² NiX₂, Ni(OR¹⁸)₂, Pd(O₂CR⁹)₂, Pd R¹⁰ COCH═C(O)R¹⁰ !₂, PdX₂, L¹ L² PdX₂, and Pd(OR¹⁹)₂ ;

said olefin is selected from the group consisting of ethylene, an olefinof the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclobutene, cyclopentene,and a norbornene;

R² and R⁵ are each independently aryl or substituted aryl, provided inboth R² and R⁵ at least one of the carbon atoms bound to a carbon atombound directly to an imino nitrogen atom does not have any hydrogenatoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a carbocyclic ring;

R¹³, R¹⁴ and R¹⁵ are each independently aryl or substituted aryl;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms; and

each R¹⁸ and R¹⁹ is independently hydrocarbyl, substituted hydrocarbyl,or R²¹ SO₃ ⁻ ;

each R⁷, R⁸, R⁹ and R¹⁰ is independently hydrocarbyl or substitutedhydrocarbyl containing from 1 to 20 carbon atoms;

each X is independently halogen or R²¹ SO₃ ⁻ ;

each R²¹ is independently aryl, substituted aryl or perfluoroalkyl;

L¹ and L² are ligands capable of being displaced by (I), or takentogether are a bidentate ligand that is capable of being displaced by(I); and

Y is a relatively noncoordinating anion;

and provided that when said hydrocarbylation compound is other than analkylaluminum compound containing one or more halogen atoms bound to analuminum atom or (R²⁰ AlO)_(q) wherein R²⁰ is alkyl and q is a positiveinteger, (II) must be present.

Described herein is a novel compound of the formula ##STR3## whereineach X is independently halogen, R⁷ CO₂, R⁸ COCH═C(O)R⁸, or OR¹⁸, eachR¹⁸ is independently hydrocarbyl, and R⁷, R⁸ are hydrocarbyl orsubstituted hydrocarbyl containing from 1 to 20 carbon atoms.

Also disclosed is a compound of the formula ##STR4##

DETAILS OF THE INVENTION

Herein certain terms are used to define certain chemical groups orcompounds. These terms are defined below.

A "hydrocarbyl group" is a univalent group containing only carbon andhydrogen. If not otherwise stated, it is preferred that hydrocarbylgroups herein contain 1 to about 30 carbon atoms.

By "substituted hydrocarbyl" herein is meant a hydrocarbyl group whichcontains one or more substituent groups which are inert under theprocess conditions to which the compound containing these groups issubjected. The substituent groups also do not substantially interferewith the process. If not otherwise stated, it is preferred thatsubstituted hydrocarbyl groups herein contain 1 to about 30 carbonatoms. Included in the meaning of "substituted" are heteroaromaticrings.

By an alkyl aluminum compound is meant a compound in which at least onealkyl group is bound to an aluminum atom. Other groups such as alkoxide,oxygen, and halogen may also be bound to aluminum atoms in the compound.

By "hydrocarbylene" herein is meant a divalent group containing onlycarbon and hydrogen. Typical hydrocarbylene groups are -(CH₂)₄ --, --CH₂CH(CH₂ CH₃)CH₂ CH₂ - and ##STR5## If not otherwise stated, it ispreferred that hydrocarbylene groups herein contain 1 to about 30 carbonatoms.

By "substituted hydrocarbylene" herein is meant a hydrocarbylene groupwhich contains one or more substituent groups which are inert under theprocess conditions to which the compound containing these groups issubjected. The substituent groups also do not substantially interferewith the process. If not otherwise stated, it is preferred thatsubstituted hydrocarbylene groups herein contain 1 to about 30 carbonatoms. Included within the meaning of "substituted" are heteroaromaticrings.

By "a norbornene" is meant that the monomer is characterized bycontaining at least one norbornene-functional group in its structureincluding norbornadiene as identified by the formulas below, which canbe substituted or unsubstituted ##STR6## wherein "a" represents a singleor double bond.

Representative monomers are compounds (XXXV) and (XXXX) as follows:##STR7## wherein R⁴⁶, R⁴⁷, R⁴⁸, and R⁴⁹ independently are hydrogenhalogen, or hydrocarbyl, provided that, except if the hydrocarbyl groupis vinyl, if any of the hydrocarbyl are alkenyl, there is no terminaldouble bond, i.e., the double bond is internal; or R⁴⁶ and R⁴⁸ takentogether can be part of carbocyclic ring (saturated, unsaturated oraromatic); or R⁴⁶ and R⁴⁷ and/or R⁴⁸ and R⁴⁹ taken together are analkylidene group. In these structures "z" is 1 to 5.

Examples of such norbornenes include norbornadiene, 2-norbornene,5-methyl-2-norbornene, 5-hexyl-2-norbornene, 5-ethylidene-2-norbornene,vinylnorbornene, dicyclopentadiene, dihydrodicyclopentadiene,tetracyclododecene, trimers of cyclopentadiene, halogenated norborneneswherein R⁴⁶, R⁴⁷, R⁴⁸ and R⁴⁹ may also be halogen or fully halogenatedalkyl groups such as C_(w) F_(2w+1) wherein w is 1 to 20, such asperfluoromethyl and perfluorodecyl.

The halogenated norbornenes can be synthesized via the Diels-Alderreaction of cyclopentadiene an appropriate dieneophile, such as F₃CC.tbd.CCF₃ or R⁴⁹ ₂ C═CR⁴⁹ C_(w) F_(2w+1) wherein each R⁴⁹ isindependently hydrogen or fluorine and w is 1 to 20.

By "saturated hydrocarbyl" is meant a univalent group containing onlycarbon and hydrogen which contains no unsaturation, such as olefinic,acetylenic, or aromatic groups. Examples of such groups include alkyland cycloalkyl. If not otherwise stated, it is preferred that saturatedhydrocarbyl groups herein contain 1 to about 30 carbon atoms.

By "aryl" is meant a monovalent radical which is one or more carbocyclicaromatic rings, and wherein the free bond is to a carbon atom of anaromatic ring. By "substituted aryl" is meant an aryl group substitutedwith one or more substituents which do not interfere with thepolymerization reaction. Phenyl is a preferred aryl group for R¹³, R¹⁴and R¹⁵.

Herein the group "OTf" means a perfluoroalkylsulfonate anion containing1 to 20 carbon atoms. A preferred perfluoroalkylsulfonate anion istrifluoromethanesulfonate (sometimes "triflate").

By "α-olefin" is meant a compound of the formula CH₂ ═CHR¹⁹, wherein R¹⁹is n-alkyl or branched n-alkyl, preferably n-alkyl.

By "linear α-olefin" is meant a compound of the formula CH₂ ═CHR¹⁹,wherein R¹⁹ is n-alkyl. It is preferred that the linear α-olefin have 4to 40 carbon atoms.

By a "saturated carbon atom" is meant a carbon atom which is bonded toother atoms by single bonds only. Not included in saturated carbon atomsare carbon atoms which are part of aromatic rings.

By a quaternary carbon atom is meant a saturated carbon atom which isnot bound to any hydrogen atoms. A preferred quaternary carbon atom isbound to four other carbon atoms.

By an olefinic bond is meant a carbon-carbon double bond, but does notinclude bonds in aromatic rings.

By a "polymerization process" herein (and the polymers made therein) ismeant a process which produces a polymer with a degree of polymerization(DP) of about 20 or more, preferably about 40 or more. By "DP" is meantthe average number of repeat (monomer) units in the polymer.

By a metal containing hydrocarbylation compound is meant a compoundwhich can transfer a hydrocarbyl group to a nickel or palladiumcompound. One form of this compound is commonly called an alkylatingagent or compound in organic chemistry. Generally the hydrocarbyl groupis thought of being present in the compound as an anion. Usefulalkylating agents have the formula MX_(m) R⁶ _(n) or Al(O)R¹¹ !_(q),wherein M is a metal, preferably Li, Mg, Zn II!, Al, or Sn IV!; each Xis independently F, Cl, Br, I, or OR¹² ; each R⁶ is independentlyhydrocarbyl containing from 1 to 20 carbon atoms; m is zero or greaterand n is 1 or greater, and m+n is the valence of M and if the valence ofM is 1, then m is 0; R¹¹ and R¹² are each independently hydrocarbyl,preferably alkyl, containing 1 to 20 carbon atoms; and q is a positiveinteger. It is preferred that R¹¹ is methyl.

By a weakly coordinating anion herein is meant an anion that does notcoordinate strongly to a nickel or palladium cationic complex. Thecoordinating ability of such anions is known and has been discussed inthe literature, see for instance W. Beck., et al., Chem. Rev., vol. 88p. 1405-1421 (1988), and S. H. Strauss, Chem. Rev., vol. 93, p. 927-942(1993), both of which are hereby included by reference. In addition tothese "traditional" weakly coordinating anions, heterogeneous anions mayalso be employed. In these cases, the true nature of the counterion ispoorly defined or unknown. A wide variety of heterogeneous inorganicmaterials can be made to function as non-coordinating counterions.Examples include aluminas, silicas, silica/aluminas, cordierites, clays,MgCl2, and many others utilized as traditional supports forZiegler-Natta olefin polymerization catalysts. These are generallymaterials which have Lewis or Bronsted acidity. High surface area isusually desired and often these materials will have been activatedthrough some heating process. Heating may remove excess surface waterand change the surface acidity from Bronsted to Lewis type. Materialswhich are not active in the role may often be made active by surfacetreatment. For instance, a surface-hydrated silica, zinc oxide or carboncan be treated with an alkylaluminum compound to provide the requiredfunctionality.

Preferred relatively noncoordinating anions are BAF, BF₄, SbF₆, B(C₆F₅)₄ and PF₆. Herein BAF is an abbreviation for the tetrakis3,5-bis(trifluoromethyl)phenyl!borate.

It is preferred that each R¹⁸ and R¹⁹ is independently hydrocarbyl, eachR⁷ , R⁸, R⁹ and R¹⁰ is independently hydrocarbyl, and/or each X isindependently halogen, more preferably chlorine or bromine. When presentit is preferred that R²¹ is trifluoromethanesulfonate, phenyl or tolyl.

In both of the polymerization processes described herein compound (I) ora complex of it is present initially. In (I) R² and R5 are eachindependently aryl or substituted aryl, provided in both R² and R⁵ atleast one of the carbon atoms bound to a carbon atom bound directly toan imino nitrogen atom does not have any hydrogen atoms bound to it. Inpractice this means that in R² and R⁵ the carbon atom ortho or adjacentto the carbon atom which is bound to an imino nitrogen atom must besubstituted. Suitable groups for R² and R⁵ include 2-methylphenyl,2-phenylphenyl, 2,6-diisoproylphenyl, 1-naphthyl, 1-methyl-2-naphthyl,1-anthracenyl, and 9-anthracenyl. Aryl groups that are not suitableinclude phenyl, 2-naphthyl, and 3-ethylphenyl.

Preferred combinations of groups for R², R³, R⁴ and R⁵ are given in thefollowing Table.

    ______________________________________                                        R.sup.2     R.sup.3    R.sup.4                                                                             R.sup.5                                          ______________________________________                                        2,6-i-PrPh  H          H     2,6-i-PrPh                                       2,6-i-PrPh  Me         Me    2,6-i-PrPh                                       2,6-i-PrPh  An         An    2,6-i-PrPh                                       2,6-MePh    H          H     2,6-MePh                                         2,6-EtPh    Me         Me    2,6-EtPh                                         2,4,6-MePh  Me         Me    2,4,6-MePh                                       2,6-MePh    Me         Me    2,6-MePh                                         2,6-MePh    An         An    2,6-MePh                                         2-t-BuPh    An         An    2-t-BuPh                                         2,5-t-BuPh  An         An    2,5-t-BuPh                                       2,4,6-MePh  An         An    2,4,6-MePh                                       2-Cl-6-MePh Me         Me    2-Cl-6-MePh                                      2,6-Cl-4-OMePh                                                                            Me         Me    2,6-Cl-4-OMePh                                   2,6-Cl-4-OMePh                                                                            An         An    2,6-Cl-4-OMePh                                   2-i-Pr-6-MePh                                                                             An         An    2-i-Pr-6-MePh                                    2-i-Pr-6-MePh                                                                             Me         Me    2-i-Pr-6-MePh                                    2,6-t-BuPh  H          H     2,6-t-BuPh                                       2,6-t-BuPh  Me         Me    2,6-t-BuPh                                       2,6-t-BuPh  An         An    2,6-t-BuPh                                       2-t-BuPh    Me         Me    2-t-BuPh                                         ______________________________________                                    

Herein Me is methyl, Et is ethyl, Pr is propyl, Bu is butyl, Ph isphenyl, OMe is methoxy, and An is 1,8-naphthylylene. Any of the groupsshown in the above table may also be mixed in any fashion to achieveother combinations.

In certain situations "unsymmetrical" α-diimine ligands of formula (I)are also preferred. In particular when R² and R⁵ are phenyl, and one orboth of these is substituted in such a way as different sized groups arepresent in the 2 and 6 position of the phenyl ring(s) unusual polymersmay be produced, for instance if one or both of R² and R⁵ are2-t-butylphenyl. In this context when R² and/or R⁵ are "substituted"phenyl the substitution may be not only in the 2 and/or 6 positions, buton any other position in the phenyl ring. For instance,2,5-di-t-butylphenyl, and 2-t-butyl-4,6-dichlorophenyl would be includedin substituted phenyl.

The steric effect of various groupings has been quantified by aparameter called E_(s), see R. W. Taft, Jr., J. Am. Chem. Soc., vol. 74,p. 3120-3128, and M. S. Newman, Steric Effects in Organic Chemistry,John Wiley & Sons, New York, 1956, p. 598-603. For the purposes herein,the E_(s) values are those for o-substituted benzoates described inthese publications. If the value for E_(s) for any particular group isnot known, it can be determined by methods described in thesepublications. For the purposes herein, the value of hydrogen is definedto be the same as for methyl. It is preferred that difference in E_(s),when R² (and preferably also R⁵) is phenyl, between the groupssubstituted in the 2 and 6 positions of the phenyl ring is at least0.15, more preferably at least about 0.20, and especially preferablyabout 0.6 or more. These phenyl groups may be unsubstituted orsubstituted in any other manner in the 3, 4 or 5 positions. Thesedifferences in E_(s) are preferred in (I), and in both of thepolymerization processes herein.

It will be understood by the artisan that not every possible compound(I) or its Ni or Pd complex will be active in polymerizations of everyolefin listed herein, but that the vast majority will be active in suchpolymerizations. Special steric or electronic features in (I) combinedwith the structure of the olefin may prevent polymerization in a fewcases. However the determination of whether a particular α-diimine orits Ni or Pd complex will be active in polymerization with a certainolefin requires minimal experimentation to determine, see for instancethe polymerization Examples herein.

Preferred olefins in both polymerizations are one or more of ethylene,propylene, 1-butene, 2-butene, 1-hexene 1-octene, 1-pentene,1-tetradecene, norbornene, and cyclopentene, with ethylene, propyleneand cyclopentene being more preferred. Ethylene and cyclopentene (aloneas homopolymers) are especially preferred. Another preferred type ofolefin is an α-olefin, and a linear α-olefin is especially preferred.When norbornene is used as a monomer it is preferred that it be the onlyolefin present.

Random copolymers may be made with these polymerization processes by thesimultaneous polymerization of 2 or more olefins. Block copolymers maybe made (particularly at subambient temperatures, preferably about -30°C. to 0° C.) by sequential polymerization of the monomer(s) of eachblock in the polymer.

It has been found that compound 4, ##STR8## when used for polymerizationof cyclopentene, gives a tractable cyclopentene with the highest meltingpoint yet achieved. X is preferably chlorine or bromine. This compoundmay be used in the first polymerization process. It is made fromcompound (VII), or (VII) may be used directly in the secondpolymerization process. ##STR9## In both 4 and (VII) the methoxy groupmay be replaced by an alkoxy group wherein the alkoxy group contains 2to 20 carbon atoms.

The temperature at which the polymerization processes are carried out isabout -100° C. to about +200° C., preferably about 0° C. to about 150°C., more preferably about 25° C. to about 100° C. The pressure at whichthe polymerization is carried out (for a gaseous monomer) is notcritical, atmospheric pressure to about 275 MPa being a suitable range.The pressure can affect the microstructure of the polyolefin produced.

A preferred compound (II) is (C₆ F₅)₃ B. When (II) is (R¹³ R¹⁴ R¹⁵ C)Yit is preferred that all of R¹³, R¹⁴ and R¹⁵ are phenyl. It will beunderstood by the artisan that (II) is preferably a Lewis acid-typecompound.

In the second polymerization process, when a hydrocarbylation compoundis other than an alkylaluminum compound containing one or more halogenatoms bound to an aluminum atom or an alkyl aluminoxane, (II) must bepresent. Thus when the hydrocarbylation compound is R₃ Al (II) must bepresent. When the hydrocarbylation compound is R₂ AlBr, RAlCl₂, or"RAlO", (II) may optionally be present (R in these last two sentences isalkyl).

In the first process, when a Ni II! or Pd II! complex of (I) is used, apreferred structure for the complex is ##STR10## wherein M is Ni or Pd,R², R³, R⁴ and R⁵ are as defined as above and T¹ and T² are eachindependently halogen, R⁷ CO₂, R⁸ COCH═C(O)R⁸, OR¹⁸ wherein R⁷, R⁸ andR¹⁸ are as defined above. It is preferred that T¹ and T² are chlorineand/or bromine.

In both polymerization processes, molar ratios of the variousingredients are not critical, but for good yields of polymer and/or tominimize cost of ingredients, certain ratios are preferred. In the firstpolymerization process it is preferred that the ratio of number of molesof olefin: "moles" of Pd or Ni present be greater that 3,000, preferablyabout 5,000 or more. The molar ratio of (II): Pd or Ni is preferablyabout 0.5 to about 10, more preferably about 1 to about 5. The molarratio of hydrocarbylation compound: Pd or Ni is preferably about 0.5 toabout 200, more preferably about 20 to about 100, in the secondpolymerization process when (II) is not present. In the firstpolymerization process, or in the second polymerization process when(II) is present, the molar ratio of hydrocarbylation compound: Pd or Niis preferably about 0.5 to about 20, more preferably about 1 to about10.

When the ingredients for the polymerization are first mixed to initiatethe polymerization it is preferred that they be mixed in a liquidmedium, preferably a liquid medium in which at least one of theingredients other than the olefin is at least slightly soluble. Forinstance the polymerization of cyclopentene may be carried out in neatcyclopentene or in a mixture of 1,2,4-trichlorobenzene and cyclopentene.The polymerization itself may then be carried out in solution (thepolymer soluble in the medium), slurry, or even the gas phase withdroplets containing the active catalyst suspended in, for example,gaseous olefin.

The polymerization may be carried out in any of the usual ways, such asa batch, semi-batch or continuous operation. The latter for example maybe a continuous stirred tank reactor, which is well known in the art.

These polymerization processes have advantages over those processesreported in L. K. Johnson, et. al., J. Am. Chem. Soc., vol. 117, p.6414-6415 (1995), and L. K. Johnson, et al., J. Am. Chem. Soc., vol.118, p. 267-268 (1996). For the first polymerization process, thepresence of (II) reduces the amount of alkylaluminum compound that mustbe added to the process to achieve good polymer yields, and/or the Ni orPd compound which is used is relatively stable and therefore may bestored for long periods and/or used under ambient conditions (e.g. norefrigeration needed). In addition to the advantages described for thefirst polymerization process, the second polymerization does not requirethe prior preparation of a complex of Ni or Pd with (I), but rather theNi or Pd compounds used are readily available and relatively stable. Nothaving to prepare the Ni or Pd complex of (I) in a separate step is alsoeconomically advantageous.

In the Examples, the following abbreviations are used:

DSC--differential scanning calorimetry

Et--ethyl

Me--methyl

MMAO--modified methyl aluminoxane

OAc--acetate

Pr--propyl

Tg--glass transition temperature

Tm--melting point

EXAMPLES

Cyclopentene was purified by passage through a column of 5 Å molecularsieves, followed by passage through a column of alumina, and finallydistillation under nitrogen from sodium metal.

Modified Methyl Aluminoxane (MeAlO)_(n) ! used in these experiments waspurchased from Akzo as a 6.7 wt. % solution in toluene. The methylaluminoxane has been modified by replacing about 25 mole percent of themethyl groups with isobutyl groups.

EXAMPLES 1-18 AND COMPARATIVE EXAMPLES A-L

The following general procedure was used with compounds 1-6 below. In anitrogen filled dry box, the catalyst was suspended in cyclopentene(molar ratio=10,000:1 unless otherwise noted). (II) and hydrocarbylationcompound (HCC) were then added in rapid succession; molar ratios basedon nickel or palladium are noted in Table 1. Unless otherwise noted,(II) was added to the reaction mixture before the HCC. The resultingmixture was stirred at ambient temperature under nitrogen; in someinstances, due to the amount of precipitated polymer it was impossibleto stir the reaction for more than a few days. After the number of daysindicated in Table 1, the reaction was quenched and the polymercompletely precipitated by addition of methanol. The polymer was thenwashed with methanol/HCl and then acetone on a fritted filter, anddried. The total turnover number for each reaction (moles cyclopentenepolymerized per mole of Ni or Pd) is indicated in Table 1.

It can be seen from Table 1 that addition of (II) such as B(C₆ F₅)₃ andAlCl₃ allows for the successful use of alkylating agents such as AlMe₃,AlEt₃, Al(OEt)Et₂, and ZnEt₂ ; in the absence of (II), no product isobserved.

DSC data for several examples are compiled in Table 2. In general, themelting points are broad and the Tm values given represent theapproximate end of the melting transition.

                  TABLE 1                                                         ______________________________________                                         ##STR11##                                                                     ##STR12##                                                                     ##STR13##                                                                     ##STR14##                                                                     ##STR15##                                                                     ##STR16##                                                                         NI or                                                                    Ex-  Pd                           turn-                                       am-  Com-    HCC         (II)     overs.sup.a                                                                          Melt                                 ple  pound   (equiv)     (equiv)  (days) Index.sup.b                          ______________________________________                                        1    1       EtalCl.sub.2 (3)                                                                          B(C.sub.6 F.sub.5).sub.3 (3)                                                           1833 (7)                                                                             7.6                                  2.sup.e                                                                            1       EtAlCl.sub.2 (3)                                                                          (Ph.sub.3 C)BF.sub.4 (3)                                                               1827 (7)                                                                             78                                   A    1       EtalCl.sub.2 (50)                                                                           --     1760 (7)                                    B    1       EtalCl.sub.2 (3)                                                                            --      846 (7)                                                                             8.4                                  3    1       AlEt.sub.3 (3)                                                                            B(C.sub.6 F.sub.5).sub.3 (3)                                                           3680 (7)                                                                             14                                   C    1       AlEt.sub.3 (3)                                                                              --       0 (5)                                     4    1       AlEt.sub.3 (3)                                                                            AlCl.sub.3 (50)                                                                        6031 (7)                                                                             high.sup.c                           5    1       AlEt.sub.3 (3)                                                                            AlCl.sub.3 (3)                                                                         1398 (7)                                                                             6.2                                  6    1       AlEt.sub.3 (3)                                                                            Al(OTf).sub.3 (50)                                                                      950 (7)                                                                             54                                   7    1       AlEt.sub.3 (3)                                                                            AlBr.sub.3 (50)                                                                        7624 (7)                                                                             high.sup.c                           8    1       AlMe.sub.3 (3)                                                                            B(C.sub.6 F.sub.5).sub.3 (3)                                                           4325 (7)                                                                             14                                   D    1       AlMe.sub.3 (50)                                                                           --         0 (7)                                     9.sup.e                                                                            1       Al(OEt)Et.sub.2 (5)                                                                       B(C.sub.6 F.sub.5).sub.3 (5)                                                           4232 (7)                                                                             9.6                                  E    1       Al(OEt)Et.sub.2 (5)                                                                         --       0 (6)                                     10   1       ZnEt.sub.2 (3)                                                                            B(C.sub.6 F.sub.5).sub.3 (3)                                                           2880 (7)                                                                             19                                   F    1       ZnEt.sub.2 (3)                                                                              --       0 (8)                                     11   2       AlEt.sub.3 (3)                                                                            B(C.sub.6 F.sub.5).sub.3 (3)                                                           5660 (7)                                                                             2.1                                  G.sup.g                                                                            2       (MeAlO).sub.n (100)                                                                         --     1195 (5)                                                                             7.6                                  12   2       EtalCl.sub.2 (3)                                                                          B(C.sub.6 F.sub.5).sub.3 (3)                                                           3250 (7)                                                                             1.7                                  H.sup.h                                                                            2       EtAlCl.sub.2 (50)                                                                           --     5230 (8)                                                                             3.6                                  13   2       AlEt.sub.3 (3)                                                                            AlCl.sub.3 (50)                                                                        4718 (7)                                                                             high.sup.c                           14.sup.e                                                                           2       Al(OEt)Et.sub.2 (5)                                                                       B(C.sub.6 F.sub.5).sub.3 (5)                                                           4688 (7)                                                                             2.4                                  15   3       AlEt.sub.3 (3)                                                                            B(C.sub.6 F.sub.5).sub.3 (3)                                                           2514 (7)                                                                             1.0                                  I    3       (MeAlO).sub.n (100)                                                                         --     2020 (7)                                    J    3       EtalCl.sub.2 (50)                                                                           --     5000 (2)                                    16   4       AlEt.sub.3 (3)                                                                            B(C.sub.6 F.sub.5).sub.3 (3)                                                           3770 (7)                                    K    4       EtalCl.sub.2 (50)                                                                           --     7210 (7)                                    L    4       (MeAlO).sub.n (100)                                                                         --      845 (7)                                    17   5       ZnEt.sub.2 (3)                                                                            B(C.sub.6 F.sub.5).sub.3 (3)                                                           3462 (7)                                                                             0.9.sup.f                            18   6       AlEt.sub.3 (3)                                                                            B(C.sub.6 F.sub.5).sub.3 (3)                                                           1243 (7)                                                                             low.sup.d                            ______________________________________                                    

^(a) "turnovers"=molar equivalents of monomer polymerized per molarequivalent of Ni or Pd ^(b) Melt indices were run with 8.5 kg weights at300° C. MI value in Table 1 is defined as the mass of polymer (in grams)extruded in 10 minutes. The orifice was 2.095 mm in dia. and 8.000 mmlong. MI value is inversely related to polymer molecular weight. ^(c)Melt index value too high to be recorded accurately; indicatesrelatively low molecular weight polymer. ^(d) Melt index value too lowto be conveniently recorded; indicates relatively high molecular weight.^(e) In this example, the alkylating agent was added to the reactionmixture before the Lewis acid. ^(f) MI recorded at 275° C. ^(g)Cyclopentene: Ni=5,000:1^(h) Cyclopentene:

                  TABLE 2                                                         ______________________________________                                        Example       ˜Tm (end) °C.                                                               ΔHf (J/g)                                      ______________________________________                                         1            285        17                                                    2            260         6                                                    B            285         8                                                    3            277        12                                                    6            280        15                                                    9            280        22                                                   10            280        24                                                   11            265        16                                                   12            255        12                                                    H            260        17                                                   14            263        15                                                   15            290        18                                                    I            291        18                                                    J            291        31                                                   16            325        32                                                    K            335         9                                                   17            275        22                                                   ______________________________________                                    

EXAMPLE 19

This example demonstrates the use of Ni(acac)₂ (acace=MeCOCH═C(O)Me) asa precursor for cyclopentene polymerization. In a nitrogen filled glovebox, Ni(acac)₂ (4 mg, 0.015 mmol) was dissolved in cyclopentene (10.0 g,147 mmol) to give a pale, green-blue solution. To this was added 7 (6mg, 0.015 mmol). To the resulting orange solution was added B(C₆ F₅)₃(23 mg, 0.045 mmol) to give a violet solution. Finally, 1.9M AlEt₃ intoluene (24 ul, 0.045 mmol) was added to the reaction mixture. Theresulting magenta solution was stirred at ambient temperature for ˜3days with a magnetic stirbar; at the end of this time the reaction couldno longer be stirred due to the amount of polycyclopentene that hadprecipitated. Seven days after the addition of AlEt₃, the reactionmixture was quenched and the polymer completely precipitated by additionof methanol under air. The precipitated polymer was washed withmethanol/HCl and then acetone, and then dried to afford 4.00 g ofpolycyclopentene. DSC: Tm(end) ≈290° C. (19 J/g). This material waspressed at 300° C. to give a clear, tough film. ##STR17##

Comparative Example M

This experiment was identical to Example 19, except that B(C₆ F₅)₃ wasnot present. Methanol was added to the reaction mixture after it hadstirred at ambient temperature for 7 days; no polycyclopenteneprecipitated. This demonstrates that (II) B(C₆ F₅)₃ in 19! must bepresent for activity when AlEt₃ is used as the alkylating agent.

EXAMPLE 20

This example further demonstrates the use of Ni(acac)₂ as a catalystprecursor. In a nitrogen filled glove box, Ni(acac)₂ (4 mg, 0.015 mmol)and 8 (5 mg, 0.015 mmol) were dissolved in cyclopentene (10.0 g, 147mmol) to give a pale-yellow solution. To this was added B(C₆ F₅)₃ (23mg, 0.045 mmol) followed by 1.9M AlEt₃ in toluene (24 ul, 0.045 mmol).The resulting orange solution was stirred at ambient temperature for 7days with a magnetic stirbar. The reaction mixture was then quenched andthe polymer completely precipitated by addition of methanol under air.The precipitated polymer was washed with methanol/HCl and then acetone,and then dried to afford 3.19 g of polycyclopentene. DSC: Tm(end) ≈270°C. (20 J/g). ##STR18##

EXAMPLE 21

This example demonstrates the use of Ni O₂ C(CH₂)₆ CH₃ !₂ as a catalystprecursor. In a nitrogen filled glove box, Ni O₂ C(CH₂)₆ CH₃ !₂ (5 mg,0.015 mmol) and 7 (6 mg, 0.015 mmol) were dissolved in cyclopentene(10.0 g, 147 mmol) to give an orange solution. To this was added B(C₆F₅)₃ (23 mg, 0.045 mmol) followed by 1.9M AlEt₃ in toluene (24 ul, 0.045mmol). The resulting magenta solution was stirred at ambient temperaturefor 7 days with a magnetic stirbar. The reaction mixture was thenquenched and the polymer completely precipitated by addition of methanolunder air. The precipitated polymer was washed with methanol/HCl andthen acetone, and then dried afford 1.6 g of polycyclopentene.

EXAMPLE 22

This example demonstrates the use of Pd(OAc)₂ (OAc is acetate) as acatalyst precursor. In a nitrogen filled glove box, Pd(OAc)₂ (3 mg,0.013 mmol) and 9 (297 mg, 0.735 mmol) were dissolved in cyclopentene(10.0 g, 147 mmol). To this was added B(C₆ F₅)₃ (23 mg, 0.045 mmol)followed by 1.9M AlEt₃ in toluene (24 ul, 0.045 mmol). The resultingcloudy, yellow solution was stirred with a magnetic stirbar at ambienttemperature. Twenty-six hours after the addition of AlEt₃, the reactionmixture was quenched and the polymer completely precipitated by additionof methanol under air. The precipitated polymer was washed withmethanol/HCl and then acetone, and then dried to afford 3.48 g ofpolycyclopentene. DSC: Tm(end)=250° C. (24 J/g); Tg=100.4° C. Thismaterial was pressed at 300° C. to give a tough film. ##STR19##

EXAMPLE 23

This example demonstrates the synthesis of ArN═C(CH₃)C(CH₃)═NAr(Ar=2,6-dichloro-4-methoxyphenyl). 2,6-dichloro-4-methoxylaniline (0.767g, 4 mmol) and biacetyl (0.172 g, 2 mmol) were combined in 10 mL ofanhydrous methanol containing 2 drops of concentrated sulfuric acid.After 48 hours, the precipitated product was isolated by filtration,washed with a 10:1 hexane/methanol mixture and dried in vacuo to give0.476 g solid (55% yield). ¹ H NMR (CD₂ Cl₂, 300 MHz): 2.1 (s, -CH₃, 6H); 3.8 (s, -OCH₃, 6 H); 7.0 (s, aromatic H, 4H).

EXAMPLE 24

This example demonstrates the preparation of (ArN═C(CH₃)C(CH₃)═NAr)NiBr₂(Ar=2,6-dichloro-4-methoxyphenyl), 3. ArN═C(CH₃)C(CH₃)═NAr(Ar=2,4,6-trimethylphenyl) (0.132 g, 0.304 mmol) was combined with NiBr₂(1,2-dimethoxyethane) (0.094 g, 0.304 mmol) in 4.6 mL of anhydrousmethylene chloride under nitrogen in a dry box. After stirring for 168hours, the solvent was decanted from the dark purple crystallineproduct. The product was washed 3×with pentane and dried in vacuo.

EXAMPLE 25

This example demonstrates the preparation of ArN═C(An)C(An)═NAr(Ar=2,6-dichloro-4-methoxyphenyl). 2,6-dichloro-4-methoxylaniline (2.18g, 11.35 mmol) and acenapthenequinone (1.03 g, 5.63 mmol) were combinedin 20 mL of anhydrous methanol containing 3 drops of concentratedsulfuric acid. After 48 hours, the precipitated product was isolated byfiltration, washed with hexane followed by methanol, and dried in vacuoto give 2.47 g solid. ¹ H NMR showed this product to be a 3:1 mixture ofthe desired diimine and the monoimine. A portion of this solid (1.89 g)was combined with 0.42 g (2.19 mmol) additional2,6-dichloro-4-methoxyaniline in a mixture of methanol (20 mL) andchloroform (5 mL) containing 2 drops of formic acid. The mixture wasrefluxed for 6 hours and then cooled to 25° C. overnight. Theprecipitated product was isolated by filtration, washed with hexanefollowed by methanol, and dried in vacuo to give 1.70 g solid. TLCshowed this to be a mixture of two compounds. A portion of the solid(1.50 g) was purified by column chromatography on silica gel 60. Thecrude material was loaded on the column as a chloroform solution, andthen eluted with toluene. The first band (0.96 g after solventevaporation) was the desired diimine. ¹ H NMR (CD₂ Cl₂, 300 MHz): 3.77,3.80, 3.88 (singlets, -OMe, total area=6.1 H); 6.8-8.3 (aromatic H,total area=9.9 H). The three methoxy peaks are consistent with isomersdue to slow rotation about the N═C bond on the NMR time scale.

EXAMPLE 26

This example demonstrates the preparation of (ArN═C(An)C(An)═NAr)NiBr₂(Ar=2,6-dichloro-4-methoxyphenyl), 4. ArN═C(An)C(An)═NAr(Ar=2,6-dichloro-4-methoxyphenyl) (0.23 g) was combined withNiBr2(1,2-dimethoxyethane) (0.136 g) in 7.5 mL of anhydrous methylenechloride. The reaction was shaken for 24 hours. About 2/3 of the solventwas removed by evaporation. The precipitated product was isolated byfiltration on a fritted glass filter, washed with pentane on the filter,and dried in vacuo.

EXAMPLE 27

This example demonstrates the synthesis of ArN═C(CH₃)C(CH₃)═NAr(Ar=2-chloro-6-methylphenyl), which was used to synthesize catalyst 2.2-Chloro-6-methylaniline (5.66 g, 40.0 mmol) biacetyl (1.72 g, 20.0mmol) were dissolved in methanol (10 mL). To this was added 2-3 drops offormic acid. The mixture was brought to reflux for 8-9 h. Solvent wasthen removed to afford an oil. The oil was purified by chromatography ona silica gel column. The first band, after solvent removal, crystallizedto give a light yellow solid. The solid was washed with small amount ofmethanol and vacuum dried to afford 0.5 g of product (7.5%) ¹ H NMR(CDCl₃): 7.3 (d, 2H); 7.15.(d, 2H); 6.98(t, 2H); 2.10 (m, 12H).

2 was prepared from (dimethoxyethane)NiBr₂ and the above ligand, in amanner analogous to that described in examples 24 and 26.

EXAMPLE 28

This Example demonstrates the synthesis of ArN═C(CH₃)C(CH₃)═NAr(Ar=2-chloro-4,6-dimethylphenyl), which was used to synthesize 5.2-Chloro-4,6-dimethylaniline (12.45 g, 80.0 mmol) and biacetyl (3.44 g,40.0 mmol) were dissolved in methanol (10 mL). To this was added 2-3drops of formic acid. The mixture was brought to reflux for overnight.Solvent was then removed to afford an oil. The oil was purified bychromatography on a silica gel column. The first band, after solventremoval, crystallized to give a yellow solid which was identified as thedesired product (0.71 g, %). ¹ H NMR (CDCl₃): 7.10 (s, 2H); 6.95 (s,2H); 2.30 (s, 6H); 2.10 (s, 6H); 2.07 (s, 6H).

5 was prepared from (dimethoxyethane)NiBr₂ and the above ligand, in amanner analogous to that described in Examples 24 and 26.

EXAMPLE 29

This example further demonstrates the use of Pd(OAc)₂ as a catalystprecursor. In a nitrogen filled glove box, Pd(OAc)₂ (3 mg, 0.013 mmol)and 10 (256 mg, 2 0.735 mmol) were dissolved in cyclopentene (10.0 g,147.0 mmol). To this was added B(C₆ F₅)₃ (23 mg, 0.045 mmol) followed by1.9M AlEt₃ in toluene (24 μl, 0.045 mmol). The reaction mixture wasstirred by a magnetic stirbar at ambient temperature for approximately 5h, after which time it could no longer be stirred due to the amount ofprecipitated polymer. Seven days after the addition of AlEt₃, thereaction mixture was quenched and the polymer completely precipitated byaddition of methanol under air. The precipitated polymer was washed withmethanol/HCl and then acetone, and then dried to afford 1.99 g ofpolycyclopentene. Melt Index on this sample under the same conditions asdescribed in Table 1 was 0.37. ##STR20##

EXAMPLE 30

This example demonstrates the use of Pd(OAc)₂ as a catalyst precursor,in the presence of MMAO as the hydrocarbylation compound. In a nitrogenfilled glove box, Pd(OAc)₂ (3 mg, 0.013 mmol) and 10 (256 mg, 0.735mmol) were dissolved in cyclopentene (10.0 g, 147.0 mmol). To this wasadded 6.7 wt. % MMAO in toluene (0.700 mL, 1.47 mmol). The reactionmixture was stirred at ambient temperature for seven days. The reactionmixture was then quenched and the polymer completely precipitated byaddition of methanol under air. The precipitated polymer was washed withmethanol/HCl and then acetone, and then dried to afford 0.47 g ofpolycyclopentene. Melt Index on this sample under the same conditions asdescribed in Table 1 was 16.

EXAMPLE 31

This example further demonstrates the use of Pd(OAc)₂ as a catalystprecursor. In a nitrogen filled glove box, Pd(OAc)₂ (3 mg, 0.013 mmol)and 11 (116 mg, 0.334 mmol) were dissolved in cyclopentene (10.0 g,147.0 mmol). To this was added B(C₆ F₅)₃ (23 mg, 0.045 mmol) followed byfollowed by 1.9 M AlEt₃ in toluene (24 μl, 0.045 mmol). The reactionmixture was stirred by a magnetic stirbar at ambient temperature; afterseveral hours it could no longer be stirred due to the amount ofprecipitated polymer. Three days after the addition of AlEt₃, thereaction mixture was quenched and the polymer completely precipitated byaddition of methanol under air. The precipitated polymer was washed withmethanol/HCl and then acetone, and then dried to afford 3.36 g ofpolycyclopentene. ##STR21##

EXAMPLE 32

This example demonstrates the use of Pd(acac)₂ acac=MeCOCH═C(O)Me! as acatalyst precursor. In a nitrogen filled glove box, Pd(acac)₂ (4-5 mg,¹⁸ 0.015 mmol) and 11 (128 mg, 0.368 mmol) were dissolved incyclopentene (10.0 g, 147.0 mmol). To this was added B(C₆ F₅)₃ (23 mg,0.045 mmol) followed by followed by 1.9M AlEt₃ in toluene (24 μl, 0.045mmol). The reaction mixture was stirred by a magnetic stirbar at ambienttemperature; after five hours it could no longer be stirred due to theamount of precipitated polymer. Three days after the addition of AlEt₃,the reaction mixture was quenched and the polymer completelyprecipitated by addition of iso-propanol and methanol under air. Theprecipitated polymer was washed with methanol/HCl and then acetone, andthen dried to afford 4.84 g of polycyclopentene.

EXAMPLE 33

This example demonstrates polymerization of 1-hexene. In a nitrogenfilled glovebox, 6 (28 mg, 0.048 mmol) was suspended in 1-hexene (2.00g, 23.8 mmol). To this was added B(C₆ F₅)₃ (73 mg, 0.14 mmol) followedby followed by 1.9M AlEt₃ in toluene (75 μl, 0.14 mmol). The reactionmixture became noticeably warm and viscous upon addition of AlEt₃. Thereaction mixture was stirred overnight and then quenched by addition ofiso-propanol under air. The polymer was completely precipitated byaddition of methanol/HCl, and dried to afford 0.69 g of poly(1-hexene)as an extremely viscous oil. Olefin end-groups could not be detected inthe room temperature ¹ H NMR spectrum of the polymer recorded in CDCl₃.

COMPARATIVE EXAMPLE N

This example was identical to Example 33, except that B(C₆ F₅)₃ was notpresent. Methanol was added to the reaction mixture after it had stirredat ambient temperature overnight; no poly(1-hexene) precipitated. Thisdemonstrates that in this reaction (II) must be present for activitywhen AlEt₃ is used as the alkylating agent.

What is claimed is:
 1. A process for the polymerization of olefins,comprising, contacting, at a temperature of about -100° C. to about+200° C., a Ni (II) or Pd (II) complex of (I), ##STR22## a metalcontaining hydrocarbylation compound, and a compound (II) selected fromthe group consisting of B(C₆ F₅)₃, AlCl₃, AlBr₃, Al(OTf)₃, and (R¹³ R¹⁴R¹⁵ C)Y, with an olefin, wherein:said olefin is selected from the groupconsisting of ethylene, an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclobutene, cyclopentene, and a norbornene; R² and R⁵ areeach independently aryl or substituted aryl, provided in both R² and R⁵at least one of the carbon atoms bound to a carbon atom bound directlyto an imino nitrogen atom does not have any hydrogen atoms bound to it;R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a carbocyclic ring; R¹³, R¹⁴ and R¹⁵are each independently aryl or substituted aryl; each R¹⁷ isindependently hydrocarbyl or substituted hydrocarbyl provided that anyolefinic bond in said olefin is separated from any other olefinic bondor aromatic ring by a quaternary carbon atom or at east two saturatedcarbon atoms; and Y is a relatively noncoordinating anion.
 2. A processfor the polymerization of olefins, comprising, contacting a Ni (II) orPd (II) salt with (I), ##STR23## a metal containing hydrocarbylationcompound, and optionally a compound (II) selected from the groupconsisting of B(C₆ F₅)₃, AlCl₃, AlBr₃, Al(OTf)₃, and (R¹³ R¹⁴ R¹⁵ C)Y,with an olefin, wherein:said Ni (II) or Pd (II) salt is selected fromthe group consisting of Ni(O₂ CR⁷)₂, Ni R⁸ COCH═C(O)R⁸ !₂, NiX₂, L¹ L²NiX₂, Ni(OR¹⁸)₂, Pd(O₂ CR⁹)₂, Pd R¹⁰ COCH═C(O)R¹⁰ !₂, PdX₂, L¹ L² PdX₂,and Pd(OR¹⁹)₂ ; said olefin is selected from the group consisting ofethylene, an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷,cyclobutene, cyclopentene, and a norbornene; R² and R⁵ are eachindependently aryl or substituted aryl, provided in both R² and R⁵ atleast one of the carbon atoms bound to a carbon atom bound directly toan imino nitrogen atom does not have any hydrogen atoms bound to it; R³and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a carbocyclic ring; R¹³, R¹⁴ and R¹⁵are each independently aryl or substituted aryl; each R¹⁷ isindependently hydrocarbyl or substituted hydrocarbyl provided that anyolefinic bond in said olefin is separated from any other olefinic bondor aromatic ring by a quaternary carbon atom or at least two saturatedcarbon atoms; each R¹⁸ and R¹⁹ is independently hydrocarbyl, substitutedhydrocarbyl, or R²¹ SO₃ ⁻ ; each R⁷, R⁸, R⁹ and R¹⁰ is independentlyhydrocarbyl or substituted hydrocarbyl containing from 1 to 20 carbonatoms; each X is independently halogen or R²¹ SO₃ ⁻ ; each R²¹ isindependently aryl, substituted aryl or perfluoroalkyl; L¹ and L² areindependently ligands capable of being displaced by (I), or takentogether are a bidentate ligand that is capable of being displaced by(I); and Y is a relatively noncoordinating anion; and provided that whensaid hydrocarbylation compound is other than an alkylaluminum compoundcontaining one or more halogen atoms bound to an aluminum atom or (R²⁰AlO)_(q) wherein R²⁰ is alkyl and q is a positive integer, (II) must bepresent.
 3. The process as recited in claim 1 or 2 wherein said olefinis ethylene.
 4. The process as recited in claim 1 or 2 wherein saidolefin is norbornene.
 5. The process as recited in claim 1 wherein saidolefin is cyclopentene.
 6. The process as recited in claim 1 or 2wherein said olefin is a linear α-olefin.
 7. The process as recited inclaim 1 or 2 wherein a random or block copolymer is produced.
 8. Theprocess as recited in claim 1 or 2 wherein said hydrocarbylationcompound is MX_(m) R⁶ _(n), wherein:M is Li, Mg, Zn II!, Al or Sn IV!;each X is independently F, Cl, Br, I, or OR¹² ; each R⁶ is independentlyhydrocarbyl containing 1 to 20 carbon atoms; m is 0 or a positiveinteger; n is an integer of 1 or more; m+n is the valence of M; and R¹²is hydrocarbyl containing 1 to 20 carbon atoms.
 9. The process asrecited in claim 1 or 2 wherein Y is BAF, BF₄, B(C₆ F₅)₄, SbF₆ or PF₆.10. The process as recited in claim 1 or 2 wherein R², R³, R⁴ and R⁵are:

    ______________________________________                                        R.sup.2     R.sup.3    R.sup.4                                                                             R.sup.5                                          ______________________________________                                        2,6-i-PrPh  H          H     2,6-i-PrPh                                       2,6-i-PrPh  Me         Me    2,6-i-PrPh                                       2,6-i-PrPh  An         An    2,6-i-PrPh                                       2,6-MePh    H          H     2,6-MePh                                         2,6-EtPh    Me         Me    2,6-EtPh                                         2,4,6-MePh  Me         Me    2,4,6-MePh                                       2,6-MePh    Me         Me    2,6-MePh                                         2,6-MePh    An         An    2,6-MePh                                         2-t-BuPh    An         An    2-t-BuPh                                         2,5-t-BuPh  An         An    2,5-t-BuPh                                       2,4,6-MePh  An         An    2,4,6-MePh                                       2-Cl-6-MePh Me         Me    2-Cl-6-MePh                                      2,6-Cl-4-OMePh                                                                            Me         Me    2,6-Cl-4-OMePh                                   2,6-Cl-4-OMePh                                                                            An         An    2,6-Cl-4-OMePh                                   2-i-Pr-6-MePh                                                                             An         An    2-i-Pr-6-MePh                                    2-i-Pr-6-MePh                                                                             Me         Me    2-i-Pr-6-MePh                                    2,6-t-BuPh  H          H     2,6-t-BuPh                                       2,6-t-BuPh  Me         Me    2,6-t-BuPh                                       2,6-t-BuPh  An         An    2,6-t-BuPh                                       2-t-BuPh    Me         Me    2-t-BuPh.                                        ______________________________________                                    


11. The process as recited in claim 1 or 2 wherein said temperature isabout 25° C. to about 100° C.
 12. The process as recited in claim 1 or 2wherein (II) is (C₆ F₅)₃ B.
 13. The process as recited in claim 1wherein said complex is ##STR24## wherein: M is Ni or Pd;T¹ and T² areeach independently halogen, R⁷ CO₂, R⁸ COCH═C(O)R⁸, or OR¹⁸ ; R² and R⁵are each independently aryl or substituted aryl, provided in both R² andR⁵ at least one of the carbon atoms bound to a carbon atom bounddirectly to an imino nitrogen atom does not have any hydrogen atomsbound to it; R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl, or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a carbocyclic ring; each R¹⁸ isindependently hydrocarbyl; and each R⁷ and R⁸ is independentlyhydrocarbyl or substituted hydrocarbyl containing from 1 to 20 carbonatoms.
 14. The process as recited in claim 1 wherein a molar ratio of(II): Pd or Ni is about 0.5 to about 10, and a molar ratio ofhydrocarbylation compound: Pd or Ni is about 0.5 to about
 20. 15. Theprocess as recited in claim 2 wherein:when (II) is present a molar ratioof (II): Pd or Ni is about 0.5 to about 10, and a molar ratio ofhydrocarbylation compound: Pd or Ni is 0.5 to about 20; and when (II) isnot present said molar ratio of hydrocarbylation compound: Pd or Ni isabout 0.5 to about
 200. 16. The process as recited in claim 13 whereinT¹ and T² are chlorine or bromine.
 17. The process as recited in claim1, 2 or 13 wherein:said hydrocarbylation compound is MX_(m) R⁶ _(n),wherein: M is Li, Mg, Zn II!, Al or Sn IV!; each X is independently F,Cl, Br, I, or OR¹² ; each R⁶ is independently hydrocarbyl containing 1to 20 carbon atoms; m is 0 or a positive integer; n is an integer of 1or more; m+n is the valence of M; and R¹² is hydrocarbyl containing 1 to20 carbon atoms; andsaid temperature is about 25° C. to about 100° C.;and (II) is (C₆ F₅)₃ B.
 18. The process as recited in claim 1, 2 or 13wherein:said hydrocarbylation compound is MX_(m) R⁶ _(n) ; M is Li, Mg,Zn II!, Al or Sn IV!; each X is independently F, Cl, Br, I, or OR¹² ;each R⁶ is independently hydrocarbyl containing 1 to 20 carbon atoms; mis 0 or a positive integer; n is an integer of 1 or more; m+n is thevalence of M; and R¹² is hydrocarbyl containing 1 to 20 carbon atoms;said temperature is about 25° C. to about 100° C.; and (II) is (C₆ F₅)₃B; and said olefin is one or more of ethylene, norbornene, cyclopentene,or a linear α-olefin.
 19. The process as recited in claim 2 wherein eachR¹⁸ and R¹⁹ is independently hydrocarbyl, each R⁷, R⁸, R⁹ and R¹⁰ isindependently hydrocarbyl, and each X is independently chlorine orbromine.